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Do molecular conductances correlate with electrochemical rate constants? Experimental insights.
Do molecular conductances correlate with electrochemical rate constants? Experimental insights.
- Source :
-
Journal of the American Chemical Society [J Am Chem Soc] 2011 May 18; Vol. 133 (19), pp. 7509-16. Date of Electronic Publication: 2011 Apr 25. - Publication Year :
- 2011
-
Abstract
- We measured single-molecule conductances for three different redox systems self-assembled onto gold by the STMBJ method and compared them with electrochemical heterogeneous rate constants determined by ultrafast voltammetry. It was observed that fast systems indeed give higher conductance. Monotonous dependency of conductance on potential reveals that large molecular fluctuations prevent the molecular redox levels to lie in between the Fermi levels of the electrodes in the nanogap configuration. Electronic coupling factors for both experimental approaches were therefore evaluated based on the superexchange mechanism theory. The results suggest that coupling is surprisingly on the same order of magnitude or even larger in conductance measurements whereas electron transfer occurs on larger distances than in transient electrochemistry.<br /> (© 2011 American Chemical Society)
Details
- Language :
- English
- ISSN :
- 1520-5126
- Volume :
- 133
- Issue :
- 19
- Database :
- MEDLINE
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 21517075
- Full Text :
- https://doi.org/10.1021/ja201042h